Anthraselenazole derivatives and process of making them



Patented July 28, 1936 ANTHRASELENAZOLE DERIVATIVES AND PROGESS OF MAKING THEM Ralph N. Lulek, Wilmington, DeL, assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware N0 Drawing. Application April 29, 1930, Serial No. 448,436. Renewed September 28, 1933 10 Glaims.

This invention relates to organic compounds and more particularly to dyestuffs and dyestuff intermediates of the anthraquinone series. Specifically, it contemplates the condensation products of 1z9-anthraselenazole-2carboXylic-acidchloride.

Nawiasky and Sauerwein (U. S. Patent 1,539,- 689 of May 26, 1925, have disclosed certain compounds of the type A-CO-NH-A where A and A represent an anthraquinone nucleus. Lulek U. S. Patent 1,705,023 of March 12, 1929) by condensing 1:9-anthrathiazole 2 carboxylic acid chloride with amino-anthraquinones has been able to produce compounds of the type At-CO-NH-A in which At represents a residue of 1:9-anthrathiazole (C0 in 2-position) and A represents an anthraquinone nucleus.

This invention has an object, the production of a series of new and valuable organic chemical compounds. Other objects are to produce new dyestuffs, new dyestufi intermediates, to devise new processes for 'the production of dyestuffs, to devise new processes for the production of dyestuff intermediates and to produce new and valuable vat colors. Other objects will appear hereinafter. a

These objects are accomplished by the present invention whereby 1:Q-anthraselenazole-Z-carboXylic-acid is condensed with amino-anthraquinones or derivatives thereof.

The productsproduced have the general formula:--

A i-i- A being an anthraquinone nucleus. In particular, the preferred compounds'are:

l--Mono-amino-anthraquinones.

2Diamino-anthraquinones.

3Aminoanthraquinones which are halogen substituted. 7

4-Diamino-anthraquinones in which one of the amino groups has been substituted with an aroyl group.

The invention will be further understood from a consideration of the following examples. The proportions are given by weight.

Example I uct may be purified by passing chlorine through the mixture at 160 C., for two hours. It is filtered at room temperature, washed with nitrobenzene and alcohol, and dried.

The product is a yellow powder and dyes cotton from a dark blue vat in yellow shade very fast to soaping, light, and chlorine. It is insoluble in water, alkali, and hydrochloric acid. The solution color in sulphuric acid is cherry red. The reaction which takes place may be illustrated by the following equation:-

N-Se

Example II Ten (10) parts of 1:9-anthraselenazole-2-car boxylic-acid-chloride are heated with 6.4 parts of beta-amino-anthraquinone at 160 C., for two hours in 400 parts of nitrobenzene. The product separates in yellow' crystals and is purified by chlorinating at 160 C., for two hours. After filtering and washing with nitrobenzene and alcohol it appears asyellow needles.

It dyes cotton in fast yellow shades from a blue hydrosulphite vat. The solution color in sulphurie acid is red. The reaction takes place according to the following equation:

l O Y r10 Example III Ten (10) parts of 1:Q-anthraselenazoIe-Z-carboxylic acid are heatedto about 100 0., with 8 parts of phosphorus pentachloride in 400 parts of nitrobenzene for'two hours. Then 3.3 parts of 1:5-diamino-anthraquinone are added and the mass stirred at 150 0., for two hours. After purifying the product by passing in chlorine at 150 C., for two hours the product isfiltered and 10 Washed with nitrobenzene and alcohol. It dissolves in concentrated sulphuric acid with red color and dyes cotton from a violet vat in fast yellow shades.

The formation of the dyestuff may be illustrated by the following equation:

N- Se v |O l q-H A I if Example IV H-III O v Example V 7 Ten (10) parts of 129 anthraselenazole-z-carboxylic acid chloride are heated with 9.9 parts r of mono-benzoyl-1:5-diamino anthraquinone' in (100 parts of nitrobenzene at 130 'C., for two Thedyestuff separates in yellow crystals 8 'JLQ V i Example VI Ten ('10) parts of1:9-anthraselenazole-Z-carboxylic-acid-chloride are heated with 7.4 parts of 1-aminorfi-chloro-anthraquinone in 300 parts of nitrobenzene at 130 C., for two hours. The

product separates in greenish-yellow crystals and After filtering and Washing with nitrobenzene and alcohol it appears as a; yellow powder, which -is purified by passing in chlorine gas at 130 C.

dissolves in sulphuric acid with a red color. This product dyes cotton froma dark blue vat in greenish-yellow shades of exceptional fastness properties. The reaction which takes place may trated by the following equation:

The new'vat colors produced according to this be illus- 7 invention dye cotton and artificial silk. in "shades,

varyingfrom greenish yellow to yellow brown,

are very fast to washing, chlorine acid, alkali and light.

As many apparent and widely different embodiments of this invention may-be made without de- I ll and which dyes cotton reddish yellow from a blue hydrosulfite vat.

2. The product which is substantially identical with that obtainable by treating about ten parts of l:9-anthraselenazo1e-2-carboxylic-acid-chloride with about 7.4 parts of l-amino-B-chloro-anthraquinone in about three hundred parts of nitrobenzene while heated to about 130 C. which probably has the formula N-Se and which dyes cotton greenish-yellow from a blue hydrosulfite vat.

3. A compound of the typein which A is an anthraquinone radical.

4. The process of producing a compound probably having the formula:

which comprises condensing mono-benzoyl-125- di-amino-anthraquinone with 1:9-anthraselena zole-Z-carboxylic acid chloride in the presence of nitrobenzene while heating to approximately 130 C.

5. The process of producing a compound probably having the formula:

which comprises condensing l-amino-S-chloroanthraquinone with 1:9-anthraselenazole-2-carboxylic acid chloride in the presence of nitrobenzene while heating to approximately 130 C.

6. .The product which is substantially identical with that obtainable by treating about ten parts of 1:9-anthraselenazole-2-carboxy1ic acid chloride with about 3.3 parts of 1:5-di-amino-anthraquinone in the presence of about 400 parts of hitrobenzene while heating to about 150 C., which probably has the formula:

and which dyes cotton yellow from a violet hydrosulphite vat.

'7. The process of producing a compound having the probable formula:

which comprises condensing 1:5-di-amino-anthra-quinone with 1:9-anthrase1enazole-2-camboxylic acid chloride, in the presence of nitrois joinedto a radical from thegroup consisting benzene while heatingtoapproximately 150 C. of

1 -N'- or and 8. A compound having the formula in which which conipr'ises" condensing ij i9-anthraselena the radical- T zo1e 2-carbony1'ch1oride with 'a member of the group consisting of l-amino-S -chloro-anthrag quinone, 1-amino-5-benzoyl-a nino anthraqui- 2Q f none and 1:5-di-amino-anthraqninone; in 'the presence of nitroebenzene while' heating to ap- V proximately 130 C p 5 i I I V i 10. Process which comprises condensing a is joined to a radical from the group consisting r1=9-anthra-selenazoler2-cerboxylic-acid-chloride org. with an"aipha amino anthraquinone by heating and I II E 0 9. The process of producing a compoundhava mixture of the two in a. liquid suspension me 7 V ing the formula in which the radical V V dium which is inert to the reactants,

e 0 I i V RALPH N. 'LULEK. 45 

